Helical Polymer as Mimetic Enzyme Catalyzing Asymmetric Aldol Reaction

• Published in: Macromolecular rapid communications. Vol. 33; no. 8; pp. 652 - 657
• Main Authors: Zhang, Dongyue, Ren, Chonglei, Yang, Wantai, Deng, Jianping
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 23.04.2012; WILEY‐VCH Verlag; Wiley
• Subjects: Aldehydes - chemistry; aldol reaction; Applied sciences; Benzaldehydes - chemistry; Biomimetic Materials - chemistry; Biomimetic Materials - metabolism; Catalysis; chiral; Circular Dichroism; Cyclohexanones - chemistry; Enzymes - metabolism; Exact sciences and technology; helical polymer; Organic polymers; Physicochemistry of polymers; Polymers - chemistry; Polymers with particular properties; Preparation, kinetics, thermodynamics, mechanism and catalysts; Solvent effect; Nitro compound; Circular dichroism spectrum; Propargylic compound; catalysis; Chiral compound; Asymmetric catalysis; Aldol condensation; Cyclohexanone; Polymeric catalyst; Helical structure; helical polymer; aldol reaction; chiral; Benzaldehyde; Acetylene derivative copolymer; Experimental study; Complex catalyst copolymerization; Functional polymer; Organic solution; Optically active copolymer; Conjugated copolymer; Preparation; Optical activity; Carboxamide; Enantiomeric excess; Enzymatic type catalysis; Catalyst activity
• ISSN: 1022-1336; 1521-3927
• DOI: 10.1002/marc.201100826

This Communication reports optically active helical substituted polyacetylenes which solely catalyzed asymmetric Aldol reaction between cyclohexanone and p‐nitrobenzaldehyde; more importantly the helical structures are found to play crucial roles in the asymmetric catalysis, with a remarkable yield and ee (both up to 80%). A synergic effect is observed between the helical structures in the polymer main chains and the pendent prolinamide moieties for successfully catalyzing the asymmetric reaction. The role of the helical polymer backbones is further verified by tuning the relative helical structure content. Synthetic helical polymers containing pendent prolineamide moieties efficiently catalyze the asymmetric aldol reaction between cyclohexanone and p‐nitrobenzaldehyde. Both the product yield and ee can be up to 80%. Helical structures in the copolymer backbones are indispensable for the asymmetric catalysis. An increase in helical structure content leads to better catalysis effects.